CN105777981A - Preparation method of pH response fluorescent polymer - Google Patents
Preparation method of pH response fluorescent polymer Download PDFInfo
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- CN105777981A CN105777981A CN201610147116.7A CN201610147116A CN105777981A CN 105777981 A CN105777981 A CN 105777981A CN 201610147116 A CN201610147116 A CN 201610147116A CN 105777981 A CN105777981 A CN 105777981A
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- 230000004044 response Effects 0.000 title claims abstract description 42
- 229920001109 fluorescent polymer Polymers 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229920000642 polymer Polymers 0.000 claims abstract description 35
- 239000000523 sample Substances 0.000 claims abstract description 13
- JLZUZNKTTIRERF-UHFFFAOYSA-N tetraphenylethylene Chemical group C1=CC=CC=C1C(C=1C=CC=CC=1)=C(C=1C=CC=CC=1)C1=CC=CC=C1 JLZUZNKTTIRERF-UHFFFAOYSA-N 0.000 claims description 23
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 16
- ROSDSFDQCJNGOL-UHFFFAOYSA-N protonated dimethyl amine Natural products CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 16
- KAHVZNKZQFSBFW-UHFFFAOYSA-N n-methyl-n-trimethylsilylmethanamine Chemical compound CN(C)[Si](C)(C)C KAHVZNKZQFSBFW-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 125000000524 functional group Chemical group 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000002189 fluorescence spectrum Methods 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 5
- 238000012360 testing method Methods 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 4
- 239000012965 benzophenone Substances 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 239000011877 solvent mixture Substances 0.000 claims description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 3
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 239000006174 pH buffer Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 11
- 230000006399 behavior Effects 0.000 abstract description 5
- 238000011160 research Methods 0.000 abstract description 5
- 229920001577 copolymer Polymers 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 11
- 230000008859 change Effects 0.000 description 9
- 239000007788 liquid Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 150000003384 small molecules Chemical class 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 230000000638 stimulation Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- YJADROSYDFWBOK-UHFFFAOYSA-N C1(=CC=CC=C1)C=1C(=C(S(C1)(C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound C1(=CC=CC=C1)C=1C(=C(S(C1)(C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1 YJADROSYDFWBOK-UHFFFAOYSA-N 0.000 description 1
- 206010011224 Cough Diseases 0.000 description 1
- -1 Hydrogen furans Chemical class 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical group C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-N mono-methylamine Natural products NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229920000208 temperature-responsive polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/14—Preparation of carboxylic acid esters from carboxylic acid halides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1408—Carbocyclic compounds
- C09K2211/1425—Non-condensed systems
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention belongs to the field of research of stimuli responsive polymers, and particularly relates to a preparation method of a pH response fluorescent polymer. The preparation method comprises the following step of leading probe micro-molecules having a fluorescent effect into a polymer with pH response, so that the pH response polymer has the fluorescent effect. Through the fluorescent behavior of detecting probe molecules, the respondent behaviors of the pH response polymer under different pH conditions are expressed by the fluorescent effect. The synthesized pH response fluorescent polymer can respond to a wider scope of pH 2-9.
Description
Technical field
The invention belongs to stimulus responsive polymers research field, particularly relate to a kind of pH response fluorescent polymer
Preparation method.
Background technology
In recent years, it is possible to response external environment change, and in real time change self performance parameter material by
Gradually paid close attention to by people.Along with the research to these intellectual materials, stimulus responsive polymers causes scientific research
Worker's keen interest, and one of become the study hotspot of functional polymer research field.
Stimulus responsive polymers (stimuli-responsive polymers) refers to self can environment to external world
Trickle physically or chemically change (pH) make respective reaction, if molecular chain configuration or dissolubility are (such as high score
Entanglement/the disentanglement of subchain, swelling/deswelling) change, even formation of chemical bond and the one of fracture
Base polymer.Extraneous physical stimulation has temperature, light, mechanical stress etc., and chemical stimulation has pH, ion strong
Degree, redox etc..Mechanism according to stimuli responsive is different, can stimulus responsive polymers be divided into following several
Type: temperature-responsive polymer, pH responsive polymer, optical Response polymer and other responses
Property polymer.
In recent years, by MOLECULE DESIGN, can be by stimulus responsive polymers at different incentive conditions by having
The functional groups showed of the respondent behavior macroscopic view of lower polymer molecular chain or strand are (as fluorescence is imitated
Should wait) it is incorporated in the polymer of various topological structure, in order to realizing stimulus responsive polymers can be by externally
The reaction macro manifestations of boundary's environmental change purpose out.
Summary of the invention
The present invention is directed to the macro manifestations of pH responsive polymer environmental change to external world, introduce a kind of new glimmering
Light probe is in the strand of pH responsive polymer, and provides its preparation method and performance characterization, obtains
The pH responsive polymer that a kind of pH response range is wider.
The technical solution adopted in the present invention is: provide a kind of pH preparation method of response fluorescent polymer, its
Processing step is as follows:
(1) the little molecule of the fluorescence probe of anamorphic zone functional group
The fluorescence probe that this step comes anamorphic zone functional group based on the fluorescent small molecule with different fluorescent effect is little
Molecule, described fluorescent small molecule should have different fluorescent effects: aggregation inducing quenching effect ACQ or gathering
Induced luminescence effect AIE.Wherein, fluorescent small molecule includes: tetraphenylethylene (TPE), hexaphenyl thiophene cough up (HPS),
Diphenylethyllene anthracene (DSA) etc..
Functional group therein is :-OH ,-COOH ,-NH2,-COX ,-COOR ,-(CO)2O-,-N=C=O,
-CHO ,-X (X is halogens) ,-CN ,-C=C-；
The initiator that the little molecule of fluorescence probe of above-mentioned band functional group can be polymerized as initiation polymer monomer,
Participate in the monomer of polymer polymerizing, and as the functional monomer being grafted on responsive polymer strand；
Below as a example by tetraphenylethylene prepares pH response fluorescent polymer for fluorescent small molecule:
First, using Mcmurry method synthesising probing needle little molecule 4-hydroxyl tetraphenyl ethylene, reaction equation is:
Wherein, reaction raw materials includes: benzophenone, 4-dihydroxy benaophenonel, zinc powder, titanium tetrachloride, four
Hydrogen furans, benzophenone, 4-dihydroxy benaophenonel, zinc powder, titanium tetrachloride, tetrahydrochysene in above-mentioned raw materials component
The mol ratio of furans is: 1.2:1:4.4:2.2.
Then, then double bond is introduced on 4-hydroxyl tetraphenyl ethylene obtained above, will 4-hydroxyl tetraphenyl ethylene
4-acryloxy tetraphenyl ethylene being synthesized with acryloyl chloride, reaction equation is:
Wherein, reaction raw materials includes: 4-hydroxyl tetraphenyl ethylene, acryloyl chloride, triethylamine (Et3N), THF is (molten
Agent), 4-hydroxyl tetraphenyl ethylene, acryloyl chloride, triethylamine (Et in said components3N) mol ratio is 1:1.2:1:
(2) the little molecule of the probe with functional group of synthesis in step (1) is introduced pH responsive polymer
In strand, obtain copolymer；
Being introduced in certain proportion in polymer by little for the fluorescence probe of synthesis molecule in step (2), fluorescence is visited
The little molecule of pin can be by responding fluorescent polymer monomer radical combined polymerization with pH, be grafted to pH response fluorescence
The first-class method of polymer chain obtains pH and responds fluorescent polymer.
By 4-acryloxy tetraphenyl ethylene and methacrylic acid N, TMSDMA N dimethylamine ethyl ester carries out combined polymerization, by glimmering
Light probe tetraphenyl ethylene group introduces polymethylacrylic acid N, and in TMSDMA N dimethylamine ethyl ester, reaction equation is:
Wherein, polymer raw material includes: 4-acryloxy tetraphenyl ethylene, methacrylic acid N, TMSDMA N dimethylamine
Ethyl ester, AIBN (initiator), toluene (solvent), 4-acryloxy tetraphenyl ethylene, first in said components
Base acrylic acid N, TMSDMA N dimethylamine ethyl ester, AIBN, toluene, wherein, 4-acryloxy and methacrylic acid N,
The ratio of TMSDMA N dimethylamine ethyl ester can regulate on demand.
As preferably, above-mentioned 4-acryloxy tetraphenyl ethylene and methacrylic acid N, TMSDMA N dimethylamine ethyl ester is carried out
Copolymerization, wherein, methacrylic acid N, TMSDMA N dimethylamine ethyl ester and the molar ratio of tetraphenyl ethylene group
For 200:1.
Above-mentioned copolymerization temperature: 65 DEG C, reaction time: 18h；
(3) fluorescence property of resulting polymers in determination step (2), and described copolymer is dissolved in difference
Fluorescence spectrum in pH environment, determines its pH response performance in different pH environment,
(it is polymerized in step (2), the copolymer of gained is dissolved in the good solvent/poor solvent mixture of different ratio
Substrate concentration [C]=1mg/mL), survey its fluorescence spectrum, then the cushioning liquid of the different pH of preparation, polymer is molten
In the cushioning liquid of these different pH, detection fluorogram (room temperature 25 DEG C mensuration), by strong to fluorescence
The comparison of degree, obtains the pH response curve of polymer, determines that polymer is at different pH rings by fluorescence intensity
Response performance in border.
Wherein, in step (3), pH response fluorescent polymer is dissolved in the good/poor solvent mixture of different ratio
In concentration be 1～5mg/mL.PH response fluorescent polymer measures it to the response performance of condition of different pH
PH buffer concentration is 1～5mg/mL.
The beneficial effect of the invention: the inventive method has synthesized a kind of new pH and responded fluorescent polymer, obtains
Polymer has wider pH and responds interval range, compares by measuring its fluorescent effect in good poor solvent,
Determine that it has typical aggregation-induced emission effect.By detecting the Fluorescence behaviour of probe molecule, pH is rung
Emergencing copolymer respondent behavior under different pH environment is showed by its fluorescent effect.
Accompanying drawing explanation
Fig. 1 is the 4-acryloxy tetraphenyl ethylene of synthesis in embodiment 1 step (2)1H-NMR spectrum.
Fig. 2 is 4-acryloxy tetraphenyl ethylene and methacrylic acid N, N-diformazan in embodiment 1 step (4)
The copolymer of amine ethyl ester fluorogram in the toluene/n-hexane mixed solvent of different ratio.
Fig. 3 (a) is 4-acryloxy tetraphenyl ethylene and methacrylic acid N, N-bis-in embodiment 1 step (4)
The copolymer of methylamine ethyl ester fluorogram in different pH cushioning liquid；
Fig. 3 (b) is 4-acryloxy tetraphenyl ethylene and methacrylic acid N, N-in embodiment 1 step (4)
The pH response curve of the copolymer of dimethylamine ethyl ester.
Detailed description of the invention
Embodiment 1
(1) by 4-hydroxy diphenyl ketone (1.9g), benzophenone (2.2g), zinc powder (2.9g), add
In two mouthfuls of flasks of 250mL, vacuumize, inflated with nitrogen 3 times, be subsequently adding 80mLTHF, be cooled to 0 DEG C, add
Enter TiCl4(2.4mL), mixture refluxes a night.It is cooled to room temperature afterwards, adds the hydrochloric acid of 80mL1mol/L,
Extract with dichloromethane, collect organic phase, use MgSO4(anhydrous) is dried, and evaporation solvent obtains crude product, slightly
Product is isolated and purified by chromatographic column further；
(2) by product (0.1g) in (1), 4mLTHF, 0.3mL triethylamine, add and be furnished with magnetic agitation
In two mouthfuls of flasks of 50mL, in ice-water bath, enter in reactant liquor with syringe dropping 0.03mL acryloyl chloride, super
Crossing 20min, stir 2h, evaporative removal THF, it is isolated and purified that product crosses chromatographic column；
(3) by product (0.02g) in (2), methacrylic acid N, TMSDMA N dimethylamine ethyl ester (1.5g), azo two is different
Butyronitrile (0.01g), toluene (2.0mL) adds in 100mL there-necked flask, and logical nitrogen is cold in 65 DEG C of oil bath pans
Solidifying backflow, reacts 18h, and product n-hexane precipitates, and is dried；
(4) by ([C]=1mg/mL) during in (3), product is dissolved in the toluene/n-hexane mixed solvent of different ratio,
First do uv-visible absorption spectroscopy, determine fluorescence spectrum excitation wavelength (wavelength is 310nm), then it is glimmering to survey it
Light spectrum.Molten by the buffering that disodium hydrogen phosphate, citric acid, sodium carbonate and sodium acid carbonate configuration pH is 2-12
Liquid, is dissolved in the polymer of synthesis in cushioning liquid, measures its fluorescence property in different pH environment, paints
Make its pH response curve.
The test of pH response fluorescent polymer and interpretation of result
Fig. 1 is the 4-acryloxy tetraphenyl ethylene of synthesis in embodiment 1 step (2)1H-NMR spectrum.1H NMR(400MHz,CDCl3,δ):7.14-7.07(m,9H),7.05-6.99(m,8H),6.88
(d,1H),6.55(d,1H),6.31-6.24(q,1H),5.99(d,1H),5.97(d,1H)。
In embodiment 1 step (3), the number-average molecular weight of the copolymer of gained is 31800, and PDI is 2.78.Purple
Outward-visible absorption spectrum determines that fluorescence spectrum excitation wavelength is 310nm.
Fig. 2 is 4-acryloxy tetraphenyl ethylene and methacrylic acid N in embodiment 1, TMSDMA N dimethylamine ethyl ester
Copolymer at the fluorogram of the toluene/hexane mixture of different ratio,
As seen from Figure 2, when water content is 40%, the fluorescence intensity of solution is more weak, along with polymer is bad molten
The increase of agent n-hexane content, the fluorescence intensity of solution is also with increase.In this explanation embodiment 1 step (3)
The polymer of synthesis has aggregation-induced emission effect.
Fig. 3 (a) is 4-acryloxy tetraphenyl ethylene and methacrylic acid N, N-in embodiment 1 step (4)
The copolymer of dimethylamine ethyl ester is at the fluorogram of the cushioning liquid of different pH (2-12)；B () is embodiment
4-acryloxy tetraphenyl ethylene and methacrylic acid N, the pH of TMSDMA N dimethylamine methacrylate copolymers in 1 step (4)
Response curve.
From Fig. 3 (a) it can be seen that at wavelength 465nm, fluorescence intensity reaches peak value, and not with pH
Change and change.PH is between 2.18-7.01, and wavelength fluorescence intensity at 465nm is relatively low, but logical
The fluorescence intensity crossed under each pH at 465nm and the relation curve of pH, such as Fig. 3 (b) embodiment 1 step
Suddenly 4-acryloxy tetraphenyl ethylene and methacrylic acid N in (4), the copolymer pH response of TMSDMA N dimethylamine ethyl ester
Shown in curve, fluorescence intensity is linear with pH, y=1.11x+7.80 (R2=0.97)；PH is at 7.01-9.12
Between, fluorescence intensity change is relatively big, the most linear, y=20.14x-124.25 (R2=0.99)；
PH is after 9.12, and fluorescence intensity slightly declines, and tends towards stability.
In sum, the pH response fluorescent polymer synthesized by the inventive method is between 2-9 at pH,
Can be responded accurately by its fluorescent effect.
Claims (9)
1. the preparation method of a pH response fluorescent polymer, it is characterised in that: described preparation method technique
Step is as follows:
(1) the little molecule of fluorescence probe of the functional functional group of anamorphic zone, concrete synthesis technique is as follows:
1. using Mcmurry method synthesising probing needle little molecule 4-hydroxyl tetraphenyl ethylene, reaction equation is:
2. double bond is introduced on the 4-hydroxyl tetraphenyl ethylene that 1. above-mentioned steps obtains, will 4-hydroxyl tetraphenyl ethylene
4-acryloxy tetraphenyl ethylene being synthesized with acryloyl chloride, reaction equation is:
(2) the little molecule of the fluorescence probe with functional functional group that step (1) is synthesized in proportion with pH
Response fluorescent polymer monomer carries out radical copolymerization, is grafted on pH response fluorescent polymer chain obtain pH
Response fluorescent polymer, polymerization technique is as follows:
By 4-acryloxy tetraphenyl ethylene and methacrylic acid N, TMSDMA N dimethylamine ethyl ester carries out combined polymerization, by glimmering
Light probe tetraphenyl ethylene group introduces polymethylacrylic acid N, and in TMSDMA N dimethylamine ethyl ester, reaction equation is:
2. pH responds the preparation method of fluorescent polymer as claimed in claim 1, it is characterised in that: step
The most described reaction raw materials is benzophenone, 4-dihydroxy benaophenonel, zinc powder, titanium tetrachloride, and mol ratio is:
1.2:1:4.4:2。
3. pH responds the preparation method of fluorescent polymer as claimed in claim 1, it is characterised in that: step
The most described reaction raw materials is 4-hydroxyl tetraphenyl ethylene, acryloyl chloride, triethylamine (Et3N), mol ratio is:
1:1.2:1。
4. pH responds the preparation method of fluorescent polymer as claimed in claim 1, it is characterised in that: step
(2) described reaction raw materials is 4-acryloxy tetraphenyl ethylene, methacrylic acid N, TMSDMA N dimethylamine ethyl ester,
AIBN, toluene.
5. pH responds the preparation method of fluorescent polymer as claimed in claim 4, it is characterised in that: described
Methacrylic acid N, the preferred molar ratio of TMSDMA N dimethylamine ethyl ester and 4-acryloxy tetraphenyl ethylene is
200:1。
6. the test side of the pH response fluorescent polymer that a preparation method as claimed in claim 1 prepares
Method, it is characterised in that: the pH of step (2) gained is responded fluorescent polymer and is dissolved in the good/bad of different ratio
In solvent mixture, survey its fluorescence spectrum and fluorescence property；Again by changing pH condition, detect its fluorescence Spectra
Figure, by the comparison to fluorescence intensity, determines the polymer response performance to condition of different pH.
7. the method for testing of pH response fluorescent polymer as claimed in claim 6, it is characterised in that: institute
Stating the pH response fluorescent polymer concentration that is dissolved in the good/poor solvent mixture of different ratio is 1～5mg/mL.
8. the method for testing of pH response fluorescent polymer as claimed in claim 6, it is characterised in that: survey
Determining pH response fluorescent polymer is 1～5mg/mL to the pH buffer concentration of the response performance of condition of different pH.
9. the method for testing of pH response fluorescent polymer as claimed in claim 6, it is characterised in that: pH
Response fluorescent polymer is 2-9 to the pH response range of condition of different pH response performance.
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